Disperse Azo Dyes

ABSTRACT

to a process for the preparation of such dyes and to their use in the dyeing or printing of semi-synthetic and, especially, synthetic hydrophobic fibre materials, more especially textile materials.

The present invention relates to disperse dyes having an acetylamino-substituted aniline coupling component, to a process for the preparation of such dyes and to their use in the dyeing or printing of semi-synthetic and, especially, synthetic hydrophobic fibre materials, more especially textile materials.

Disperse azo dyes derived from a nitroaniline diazo component and an acetylaminoaniline coupling component have been known for a long time, for example from FR 2008404, and are used in the dyeing of hydrophobic fibre materials. It has been found, however, that the dyeings or prints obtained using the dyes known at present do not in all cases meet current requirements, especially with regard to their fastness properties in respect of light, washing and perspiration. Particularly in the field of blue dyes there is a need for new dyes that give dyeings in brilliant shades having good fastness properties in respect of light, washing and perspiration.

It has now been found, surprisingly, that the dyes according to the invention meet the criteria mentioned above to a great extent.

The present invention accordingly relates to disperse dyes that yield dyeings having very good fastness to light, to washing and to perspiration and, in addition, exhibit good build-up both in the exhaust and thermosol processes and in textile printing.

The dyes according to the invention correspond to formula

wherein

R₁ is bromo, nitro, cyano, methyl, methoxy or trifluoromethyl;

R₂ is hydrogen, chloro, bromo or trifluoromethyl;

R₃ is hydrogen, chloro, bromo, methoxy, trifluoromethyl, nitro or cyano; and

R₄ is methyl, ethyl, n-propyl, 2-methoxyethyl, methoxycarbonylmethyl or 2-methoxycarbonylethyl;

with the proviso that R₁ is cyano in case R₂ denotes chloro or bromo and R₁ is cyano or nitro in case R₂ denotes trifluoromethyl.

In formula (1) R₁ is preferably cyano.

Further preferred are dyes of formula (1) wherein R₂ is chloro.

Special preference is given to dyes of formula (1) wherein R₃ is hydrogen.

R₄ in formula (1) is preferably methyl, ethyl, methoxycarbonylmethyl or 2-methoxycarbonylethyl.

The invention also relates to a process for the preparation of a dye of formula (1) as defined above, which comprises diazotising a compound of formula

and coupling the diazonium compound so obtained to a coupling component of formula

wherein R₁, R₂, R₃ and R₄ have the meanings given for formula (1) above.

The diazo components of formula (2) as well as the coupling components of formula (3) are known or can be prepared in a manner known per se. Some are commercially available.

The diazotisation is carried out in a manner known per se, for example with sodium nitrite in an acidic, e.g. hydrochloric-acid-containing or sulfuric-acid-containing, aqueous medium. The diazotisation may, however, also be carried out using other diazotisation agents, for example using nitrosylsulfuric acid. In the diazotisation, an additional acid may be present in the reaction medium, for example phosphoric acid, sulfuric acid, acetic acid, propionic acid or hydrochloric acid or a mixture of such acids, for example a mixture of propionic acid and acetic acid. The diazotisation is advantageously carried out at temperatures of from −10 to 30° C., for example from −10° C. to room temperature.

The coupling of the diazotised compound to the coupling component of formula (3) is likewise effected in known manner, for example in an acidic, aqueous or aqueous-organic medium, advantageously at temperatures of from −10 to 30° C., especially below 10° C. Examples of acids used are hydrochloric acid, acetic acid, propionic acid, sulfuric acid and phosphoric acid.

The present invention further relates to a dye mixture comprising at least one dye of formula (1) as defined above and at least one further dye selected from the group consisting of C.I. Disperse Blue 60, C.I. Disperse Blue 79:1, C.I. Disperse Blue 72:2, C.I. Disperse Blue 148, C.I. Disperse Blue 149, C.I. Disperse Blue 165, C.I. Disperse Blue 165:1, C.I. Disperse Blue 207, C.I. Disperse Blue 284, C.I. Disperse Blue 295, C.I. Disperse Blue 316, C.I. Disperse Blue 337, C.I. Disperse Blue 354, C.I. Disperse Blue 366, C.I. Disperse Blue 367, C.I. Disperse Blue 368, C.I. Disperse Blue 376, C.I. Disperse Blue 378, C.I. Disperse Blue 380, C.I. Disperse Green 9, C.I. Disperse Violet 107, the compounds of formulas (101)-(179) described in WO 2014/016072, the compounds of formulas (101)-(106) described in WO 2009/013122 and the compounds of formulas II-2, II-3, II-4 and III-1-III-8 described in CN 101955691.

The dye mixtures according to the invention can be prepared, for example, by simply mixing the individual dyes.

The amount of the individual dyes in the dye mixtures according to the invention can vary within a wide range.

The dye mixtures according to the invention advantageously contain at least 20% by weight, preferably at least 30% by weight and especially at least 40% by weight, of one or more dyes of formula (1).

The dyes and dye mixtures according to the invention can be used in the dyeing or printing of semi-synthetic and, especially, synthetic hydrophobic fibre materials, more especially textile materials. Textile materials composed of blends that contain such semi-synthetic and/or synthetic hydrophobic fibre materials can likewise be dyed or printed using the dyes or dye mixtures according to the invention.

Semi-synthetic fibre materials that come into consideration are especially cellulose 2% acetate and cellulose triacetate.

Synthetic hydrophobic fibre materials consist especially of linear, aromatic polyesters, for example those of terephthalic acid and glycols, especially ethylene glycol, or condensation products of terephthalic acid and 1,4-bis(hydroxymethyl)cyclohexane; of polycarbonates, for example those of α,α-dimethyl-4,4-dihydroxy-diphenylmethane and phosgene, and of fibres based on polyvinyl chloride and on polyamide.

The application of the dyes and dye mixtures according to the invention to the fibre materials is effected in accordance with known dyeing procedures. For example, polyester fibre materials are dyed in the exhaust process from an aqueous dispersion in the presence of customary anionic or non-ionic dispersants and optionally customary swelling agents (carriers) at temperatures of from 80 to 140° C. Cellulose 2% acetate is dyed preferably at from 65 to 85° C. and cellulose triacetate at temperatures of from 65 to 115° C.

The dyes and dye mixtures according to the invention will not colour wool and cotton present at the same time in the dyebath or will colour such materials only slightly (very good reservation), so that they can also be used satisfactorily in the dyeing of polyester/wool and polyester/cellulosic fibre blend fabrics.

The dyes and dye mixtures according to the invention are suitable for dyeing in accordance with the thermosol process, in the exhaust process and for printing processes like screen printing or ink-jet printing.

The said fibre materials can be in a variety of processing forms, e.g. in the form of fibres, yarns or non-wovens, in the form of woven fabrics or knitted fabrics.

It is advantageous to convert the dyes and dye mixtures according to the invention into a dye preparation prior to use. For that purpose, the dye is ground so that its particle size is on average from 0.1 to 10 microns. The grinding can be carried out in the presence of dispersants. For example, the dried dye is ground with a dispersant or is kneaded in paste form with a dispersant and then dried in vacuo or by atomisation. The preparations so obtained can be used, after the addition of water, to prepare print pastes and dyebaths.

For printing, the customary thickeners will be used, e.g. modified or unmodified natural products, for example alginates, British gum, gum arabic, crystal gum, locust bean flour, tragacanth, carboxymethylcellulose, hydroxyethylcellulose, starch or synthetic products, for example polyacrylamides, polyacrylic acid or copolymers thereof, or polyvinyl alcohols.

The dyes and dye mixtures according to the invention impart to the mentioned materials, especially to polyester materials, level colour shades having very good in-use fastness properties, such as, especially, good fastness to light, to thermofixing, to pleating, to chlorine and to wetting, such as fastness to water, to perspiration and to washing; the finished dyeings are also distinguished by very good fastness to rubbing. Special mention should be made of the good fastness properties of the resulting dyeings in respect of light, perspiration and, especially, washing.

The dyes and dye mixtures according to the invention can also be used satisfactorily in the preparation of mixed shades together with other dyes.

The dyes and dye mixtures according to the invention are also very suitable for dyeing hydrophobic fibre materials from supercritical CO₂.

The present invention relates also to the above-mentioned use of the dyes and dye mixtures according to the invention as well as to a process for the dyeing or printing of semi-synthetic or synthetic hydrophobic fibre materials, especially textile materials, wherein a dye according to the invention is applied to the said materials or is incorporated into those materials. The said hydrophobic fibre materials are preferably textile polyester materials. Further substrates that can be treated by the process according to the invention as well as preferred process conditions can be found above in the detailed description of the use of the dyes according to the invention.

The invention relates also to hydrophobic fibre materials, especially polyester textile materials, dyed or printed by the said process.

The dyes according to the invention are also suitable for modern reproduction processes, for example thermotransfer printing.

The following Examples serve to illustrate the invention. In the Examples, unless otherwise indicated, parts are parts by weight and percentages are percent by weight. The temperatures are given in degrees Celsius. The relationship between parts by weight and parts by volume is the same as that between grams and cubic centimetres.

RT=room temperature

I. PREPARATION EXAMPLES Example 1.1

A. Diazotation

20 g of conc. sulfuric acid are placed in a laboratory reaction apparatus. After addition of 5 g ice the solution is cooled to RT. At this temperature, 6.01 g of 2-bromo-4-nitro-6-cyanoaniline are added. After being stirred for 30 min at RT and cooling down to 10° C., 8.2 g of 40% nitrosylsulfuric acid are added dropwise. The reaction mixture is stirred for a further 60 min at 10° C. Afterwards, the excess nitrite is destroyed by addition of sulfamic acid.

B. Coupling

7.83 g of finely powdered N-3-nitrobenzyl-N-ethyl-3-acetylaminoaniline prepared according to the method described in Example la of FR 2008404 are suspended in 10 ml ethanol and mixed with 20 g of ice.

Under stirring the solution of the diazonium salt obtained in step A is added dropwise within 60 min. The reaction mixture is stirred at RT over night. After filtration, washing and drying 11.75 g (83%) of the dye of formula (101) are obtained.

The dyes (102)-(1252) listed in Table 1 are prepared analogously to the process described in Example 1.1.

TABLE 1 (1)

(λ_(max) = wavelength of the absorption maximum) Compound R₁ R₂ R₃ R₄ λ_(max)/nm 101 CN Br m-NO₂ —C₂H₅ 573 102 CN Br m-NO₂ —CH₃ 103 CN Br m-NO₂ n-C₃H₇ 104 CN Br m-NO₂ —CH₂CH₂OCH₃ 105 CN Br m-NO₂ —CH₂CO—OCH₃ 106 CN Br m-CF₃ —CH₂CH₂CO—OCH₃ 107 CN Br m-CF₃ —CH₃ 108 CN Br m-CF₃ —C₂H₅ 109 CN Br m-CF₃ n-C₃H₇ 110 CN Br m-CF₃ —CH₂CH₂OCH₃ 111 CN Br m-CF₃ —CH₂CO—OCH₃ 112 CN Br m-CF₃ —CH₂CH₂CO—OCH₃ 113 CN Br p-OCH₃ —CH₃ 114 CN Br p-OCH₃ —C₂H₅ 115 CN Br p-OCH₃ n-C₃H₇ 116 CN Br p-OCH₃ —CH₂CH₂OCH₃ 117 CN Br p-OCH₃ —CH₂CO—OCH₃ 118 CN Br p-OCH₃ —CH₂CH₂CO—OCH₃ 119 CN Br p-CN —CH₃ 120 CN Br p-CN —C₂H₅ 121 CN Br p-CN n-C₃H₇ 122 CN Br p-CN —CH₂CH₂OCH₃ 123 CN Br p-CN —CH₂CO—OCH₃ 124 CN Br p-CN —CH₂CH₂CO—OCH₃ 125 CN Br p-Cl —CH₃ 126 CN Br p-Cl —C₂H₅ 127 CN Br p-Cl n-C₃H₇ 128 CN Br p-Cl —CH₂CH₂OCH₃ 129 CN Br p-Cl —CH₂CO—OCH₃ 130 CN Br p-Cl —CH₂CH₂CO—OCH₃ 131 CN Br p-Br —CH₃ 132 CN Br p-Br —C₂H₅ 133 CN Br p-Br n-C₃H₇ 134 CN Br p-Br —CH₂CH₂OCH₃ 135 CN Br p-Br —CH₂CO—OCH₃ 136 CN Br p-Br —CH₂CH₂CO—OCH₃ 137 CN Br p-NO₂ —CH₃ 138 CN Br p-NO₂ —C₂H₅ 139 CN Br p-NO₂ n-C₃H₇ 140 CN Br p-NO₂ —CH₂CH₂OCH₃ 141 CN Br p-NO₂ —CH₂CO—OCH₃ 142 CN Br p-NO₂ —CH₂CH₂CO—OCH₃ 143 CN Br H —CH₃ 578 144 CN Br H —C₂H₅ 582 145 CN Br H n-C₃H₇ 587 146 CN Br H —CH₂CH₂OCH₃ 572 147 CN Br H —CH₂CO—OCH₃ 555 148 CN Br H —CH₂CH₂CO—OCH₃ 571 149 CN Cl m-NO₂ —CH₃ 150 CN Cl m-NO₂ —C₂H₅ 151 CN Cl m-NO₂ n-C₃H₇ 152 CN Cl m-NO₂ —CH₂CH₂OCH₃ 153 CN Cl m-NO₂ —CH₂CO—OCH₃ 154 CN Cl m-CF₃ —CH₂CH₂CO—OCH₃ 155 CN Cl m-CF₃ —CH₃ 156 CN Cl m-CF₃ —C₂H₅ 157 CN Cl m-CF₃ n-C₃H₇ 158 CN Cl m-CF₃ —CH₂CH₂OCH₃ 159 CN Cl m-CF₃ —CH₂CO—OCH₃ 160 CN Cl m-CF₃ —CH₂CH₂CO—OCH₃ 161 CN Cl p-OCH₃ —CH₃ 162 CN Cl p-OCH₃ —C₂H₅ 163 CN Cl p-OCH₃ n-C₃H₇ 164 CN Cl p-OCH₃ —CH₂CH₂OCH₃ 165 CN Cl p-OCH₃ —CH₂CO—OCH₃ 166 CN Cl p-OCH₃ —CH₂CH₂CO—OCH₃ 167 CN Cl p-CN —CH₃ 168 CN Cl p-CN —C₂H₅ 169 CN Cl p-CN n-C₃H₇ 170 CN Cl p-CN —CH₂CH₂OCH₃ 171 CN Cl p-CN —CH₂CO—OCH₃ 172 CN Cl p-CN —CH₂CH₂CO—OCH₃ 173 CN Cl p-Cl —CH₃ 174 CN Cl p-Cl —C₂H₅ 175 CN Cl p-Cl n-C₃H₇ 176 CN Cl p-Cl —CH₂CH₂OCH₃ 177 CN Cl p-Cl —CH₂CO—OCH₃ 178 CN Cl p-Cl —CH₂CH₂CO—OCH₃ 179 CN Cl p-Br —CH₃ 180 CN Cl p-Br —C₂H₅ 181 CN Cl p-Br n-C₃H₇ 182 CN Cl p-Br —CH₂CH₂OCH₃ 183 CN Cl p-Br —CH₂CO—OCH₃ 184 CN Cl p-Br —CH₂CH₂CO—OCH₃ 185 CN Cl p-NO₂ —CH₃ 186 CN Cl p-NO₂ —C₂H₅ 187 CN Cl p-NO₂ n-C₃H₇ 188 CN Cl p-NO₂ —CH₂CH₂OCH₃ 189 CN Cl p-NO₂ —CH₂CO—OCH₃ 550 190 CN Cl p-NO₂ —CH₂CH₂CO—OCH₃ 565 191 CN Cl H —CH₃ 578 192 CN Cl H —C₂H₅ 585 193 CN Cl H n-C₃H₇ 590 194 CN Cl H —CH₂CH₂OCH₃ 577 195 CN Cl H —CH₂CO—OCH₃ 560 196 CN Cl H —CH₂CH₂CO—OCH₃ 570 197 CN CF₃ m-NO₂ —CH₃ 198 CN CF₃ m-NO₂ —C₂H₅ 199 CN CF₃ m-NO₂ n-C₃H₇ 200 CN CF₃ m-NO₂ —CH₂CH₂OCH₃ 201 CN CF₃ m-NO₂ —CH₂CO—OCH₃ 202 CN CF₃ m-CF₃ —CH₂CH₂CO—OCH₃ 203 CN CF₃ m-CF₃ —CH₃ 204 CN CF₃ m-CF₃ —C₂H₅ 205 CN CF₃ m-CF₃ n-C₃H₇ 206 CN CF₃ m-CF₃ —CH₂CH₂OCH₃ 207 CN CF₃ m-CF₃ —CH₂CO—OCH₃ 208 CN CF₃ m-CF₃ —CH₂CH₂CO—OCH₃ 209 CN CF₃ p-OCH₃ —CH₃ 210 CN CF₃ p-OCH₃ —C₂H₅ 211 CN CF₃ p-OCH₃ n-C₃H₇ 212 CN CF₃ p-OCH₃ —CH₂CH₂OCH₃ 213 CN CF₃ p-OCH₃ —CH₂CO—OCH₃ 214 CN CF₃ p-OCH₃ —CH₂CH₂CO—OCH₃ 215 CN CF₃ p-CN —CH₃ 216 CN CF₃ p-CN —C₂H₅ 217 CN CF₃ p-CN n-C₃H₇ 218 CN CF₃ p-CN —CH₂CH₂OCH₃ 219 CN CF₃ p-CN —CH₂CO—OCH₃ 220 CN CF₃ p-CN —CH₂CH₂CO—OCH₃ 221 CN CF₃ p-Cl —CH₃ 222 CN CF₃ p-Cl —C₂H₅ 223 CN CF₃ p-Cl n-C₃H₇ 224 CN CF₃ p-Cl —CH₂CH₂OCH₃ 225 CN CF₃ p-Cl —CH₂CO—OCH₃ 226 CN CF₃ p-Cl —CH₂CH₂CO—OCH₃ 227 CN CF₃ p-Br —CH₃ 228 CN CF₃ p-Br —C₂H₅ 229 CN CF₃ p-Br n-C₃H₇ 230 CN CF₃ p-Br —CH₂CH₂OCH₃ 231 CN CF₃ p-Br —CH₂CO—OCH₃ 232 CN CF₃ p-Br —CH₂CH₂CO—OCH₃ 233 CN CF₃ p-NO₂ —CH₃ 234 CN CF₃ p-NO₂ —C₂H₅ 235 CN CF₃ p-NO₂ n-C₃H₇ 236 CN CF₃ p-NO₂ —CH₂CH₂OCH₃ 237 CN CF₃ p-NO₂ —CH₂CO—OCH₃ 238 CN CF₃ p-NO₂ —CH₂CH₂CO—OCH₃ 239 CN CF₃ H —CH₃ 240 CN CF₃ H —C₂H₅ 241 CN CF₃ H n-C₃H₇ 242 CN CF₃ H —CH₂CH₂OCH₃ 242 CN CF₃ H —CH₂CO—OCH₃ 244 CN CF₃ H —CH₂CH₂CO—OCH₃ 245 CN H m-NO₂ —CH₃ 246 CN H m-NO₂ —C₂H₅ 247 CN H m-NO₂ n-C₃H₇ 248 CN H m-NO₂ —CH₂CH₂OCH₃ 249 CN H m-NO₂ —CH₂CO—OCH₃ 250 CN H m-CF₃ —CH₂CH₂CO—OCH₃ 251 CN H m-CF₃ —CH₃ 252 CN H m-CF₃ —C₂H₅ 253 CN H m-CF₃ n-C₃H₇ 254 CN H m-CF₃ —CH₂CH₂OCH₃ 255 CN H m-CF₃ —CH₂CO—OCH₃ 256 CN H m-CF₃ —CH₂CH₂CO—OCH₃ 257 CN H p-OCH₃ —CH₃ 258 CN H p-OCH₃ —C₂H₅ 259 CN H p-OCH₃ n-C₃H₇ 260 CN H p-OCH₃ —CH₂CH₂OCH₃ 261 CN H p-OCH₃ —CH₂CO—OCH₃ 262 CN H p-OCH₃ —CH₂CH₂CO—OCH₃ 263 CN H p-CN —CH₃ 264 CN H p-CN —C₂H₅ 265 CN H p-CN n-C₃H₇ 266 CN H p-CN —CH₂CH₂OCH₃ 267 CN H p-CN —CH₂CO—OCH₃ 268 CN H p-CN —CH₂CH₂CO—OCH₃ 269 CN H p-Cl —CH₃ 270 CN H p-Cl —C₂H₅ 271 CN H p-Cl n-C₃H₇ 272 CN H p-Cl —CH₂CH₂OCH₃ 273 CN H p-Cl —CH₂CO—OCH₃ 274 CN H p-Cl —CH₂CH₂CO—OCH₃ 275 CN H p-Br —CH₃ 276 CN H p-Br —C₂H₅ 277 CN H p-Br n-C₃H₇ 278 CN H p-Br —CH₂CH₂OCH₃ 279 CN H p-Br —CH₂CO—OCH₃ 280 CN H p-Br —CH₂CH₂CO—OCH₃ 281 CN H p-NO₂ —CH₃ 282 CN H p-NO₂ —C₂H₅ 283 CN H p-NO₂ n-C₃H₇ 284 CN H p-NO₂ —CH₂CH₂OCH₃ 285 CN H p-NO₂ —CH₂CO—OCH₃ 286 CN H p-NO₂ —CH₂CH₂CO—OCH₃ 287 CN H H —CH₃ 288 CN H H —C₂H₅ 545 289 CN H H n-C₃H₇ 290 CN H H —CH₂CH₂OCH₃ 291 CN H H —CH₂CO—OCH₃ 292 CN H H —CH₂CH₂CO—OCH₃ 293 NO₂ CF₃ m-NO₂ —CH₃ 294 NO₂ CF₃ m-NO₂ —C₂H₅ 295 NO₂ CF₃ m-NO₂ n-C₃H₇ 296 NO₂ CF₃ m-NO₂ —CH₂CH₂OCH₃ 297 NO₂ CF₃ m-NO₂ —CH₂CO—OCH₃ 298 NO₂ CF₃ m-CF₃ —CH₂CH₂CO—OCH₃ 299 NO₂ CF₃ m-CF₃ —CH₃ 300 NO₂ CF₃ m-CF₃ —C₂H₅ 301 NO₂ CF₃ m-CF₃ n-C₃H₇ 302 NO₂ CF₃ m-CF₃ —CH₂CH₂OCH₃ 303 NO₂ CF₃ m-CF₃ —CH₂CO—OCH₃ 304 NO₂ CF₃ m-CF₃ —CH₂CH₂CO—OCH₃ 305 NO₂ CF₃ p-OCH₃ —CH₃ 306 NO₂ CF₃ p-OCH₃ —C₂H₅ 307 NO₂ CF₃ p-OCH₃ n-C₃H₇ 308 NO₂ CF₃ p-OCH₃ —CH₂CH₂OCH₃ 309 NO₂ CF₃ p-OCH₃ —CH₂CO—OCH₃ 310 NO₂ CF₃ p-OCH₃ —CH₂CH₂CO—OCH₃ 311 NO₂ CF₃ p-CN —CH₃ 312 NO₂ CF₃ p-CN —C₂H₅ 313 NO₂ CF₃ p-CN n-C₃H₇ 314 NO₂ CF₃ p-CN —CH₂CH₂OCH₃ 315 NO₂ CF₃ p-CN —CH₂CO—OCH₃ 316 NO₂ CF₃ p-CN —CH₂CH₂CO—OCH₃ 317 NO₂ CF₃ p-Cl —CH₃ 318 NO₂ CF₃ p-Cl —C₂H₅ 319 NO₂ CF₃ p-Cl n-C₃H₇ 320 NO₂ CF₃ p-Cl —CH₂CH₂OCH₃ 321 NO₂ CF₃ p-Cl —CH₂CO—OCH₃ 322 NO₂ CF₃ p-Cl —CH₂CH₂CO—OCH₃ 323 NO₂ CF₃ p-Br —CH₃ 324 NO₂ CF₃ p-Br —C₂H₅ 325 NO₂ CF₃ p-Br n-C₃H₇ 326 NO₂ CF₃ p-Br —CH₂CH₂OCH₃ 327 NO₂ CF₃ p-Br —CH₂CO—OCH₃ 328 NO₂ CF₃ p-Br —CH₂CH₂CO—OCH₃ 329 NO₂ CF₃ p-NO₂ —CH₃ 330 NO₂ CF₃ p-NO₂ —C₂H₅ 331 NO₂ CF₃ p-NO₂ n-C₃H₇ 332 NO₂ CF₃ p-NO₂ —CH₂CH₂OCH₃ 333 NO₂ CF₃ p-NO₂ —CH₂CO—OCH₃ 334 NO₂ CF₃ p-NO₂ —CH₂CH₂CO—OCH₃ 335 NO₂ CF₃ H —CH₃ 336 NO₂ CF₃ H —C₂H₅ 337 NO₂ CF₃ H n-C₃H₇ 338 NO₂ CF₃ H —CH₂CH₂OCH₃ 339 NO₂ CF₃ H —CH₂CO—OCH₃ 340 NO₂ CF₃ H —CH₂CH₂CO—OCH₃ 341 NO₂ H m-NO₂ —CH₃ 342 NO₂ H m-NO₂ —C₂H₅ 343 NO₂ H m-NO₂ n-C₃H₇ 344 NO₂ H m-NO₂ —CH₂CH₂OCH₃ 345 NO₂ H m-NO₂ —CH₂CO—OCH₃ 346 NO₂ H m-CF₃ —CH₂CH₂CO—OCH₃ 347 NO₂ H m-CF₃ —CH₃ 348 NO₂ H m-CF₃ —C₂H₅ 349 NO₂ H m-CF₃ n-C₃H₇ 350 NO₂ H m-CF₃ —CH₂CH₂OCH₃ 351 NO₂ H m-CF₃ —CH₂CO—OCH₃ 352 NO₂ H m-CF₃ —CH₂CH₂CO—OCH₃ 353 NO₂ H p-OCH₃ —CH₃ 354 NO₂ H p-OCH₃ —C₂H₅ 355 NO₂ H p-OCH₃ n-C₃H₇ 356 NO₂ H p-OCH₃ —CH₂CH₂COH₃ 357 NO₂ H p-OCH₃ —CH₂CO—OCH₃ 358 NO₂ H p-OCH₃ —CH₂CH₂CO—OCH₃ 359 NO₂ H p-CN —CH₃ 360 NO₂ H p-CN —C₂H₅ 361 NO₂ H p-CN n-C₃H₇ 362 NO₂ H p-CN —CH₂CH₂COH₃ 363 NO₂ H p-CN —CH₂CO—OCH₃ 364 NO₂ H p-CN —CH₂CH₂CO—OCH₃ 365 NO₂ H p-Cl —CH₃ 366 NO₂ H p-Cl —C₂H₅ 367 NO₂ H p-Cl n-C₃H₇ 368 NO₂ H p-Cl —CH₂CH₂OCH₃ 369 NO₂ H p-Cl —CH₂CO—OCH₃ 370 NO₂ H p-Cl —CH₂CH₂CO—OCH₃ 371 NO₂ H p-Br —CH₃ 372 NO₂ H p-Br —C₂H₅ 373 NO₂ H p-Br n-C₃H₇ 874 NO₂ H p-Br —CH₂CH₂OCH₃ 375 NO₂ H p-Br —CH₂CO—OCH₃ 376 NO₂ H p-Br —CH₂CH₂CO—OCH₃ 377 NO₂ H p-NO₂ —CH₃ 378 NO₂ H p-NO₂ —C₂H₅ 379 NO₂ H p-NO₂ n-C₃H₇ 380 NO₂ H p-NO₂ —CH₂CH₂OCH₃ 381 NO₂ H p-NO₂ —CH₂CO—OCH₃ 382 NO₂ H p-NO₂ —CH₂CH₂CO—OCH₃ 383 NO₂ H H —CH₃ 384 NO₂ H H —C₂H₅ 540 385 NO₂ H H n-C₃H₇ 386 NO₂ H H —CH₂CH₂OCH₃ 387 NO₂ H H —CH₂CO—OCH₃ 388 NO₂ H H —CH₂CH₂CO—OCH₃ 389 CH₃ H m-NO₂ —CH₃ 390 CH₃ H m-NO₂ —C₂H₅ 391 CH₃ H m-NO₂ n-C₃H₇ 392 CH₃ H m-NO₂ —CH₂CH₂OCH₃ 393 CH₃ H m-NO₂ —CH₂CO—OCH₃ 394 CH₃ H m-CF₃ —CH₂CH₂CO—OCH₃ 395 CH₃ H m-CF₃ —CH₃ 396 CH₃ H m-CF₃ —C₂H₅ 397 CH₃ H m-CF₃ n-C₃H₇ 398 CH₃ H m-CF₃ —CH₂CH₂OCH₃ 399 CH₃ H m-CF₃ —CH₂CO—OCH₃ 400 CH₃ H m-CF₃ —CH₂CH₂CO—OCH₃ 401 CH₃ H p-OCH₃ —CH₃ 402 CH₃ H p-OCH₃ —C₂H₅ 403 CH₃ H p-OCH₃ n-C₃H₇ 404 CH₃ H p-OCH₃ —CH₂CH₂OCH₃ 405 CH₃ H p-OCH₃ —CH₂CO—OCH₃ 406 CH₃ H p-OCH₃ —CH₂CH₂CO—OCH₃ 407 CH₃ H p-CN —CH₃ 408 CH₃ H p-CN —C₂H₅ 409 CH₃ H p-CN n-C₃H₇ 410 CH₃ H p-CN —CH₂CH₂OCH₃ 411 CH₃ H p-CN —CH₂CO—OCH₃ 412 CH₃ H p-CN —CH₂CH₂CO—OCH₃ 413 CH₃ H p-Cl —CH₃ 414 CH₃ H p-Cl —C₂H₅ 415 CH₃ H p-Cl n-C₃H₇ 416 CH₃ H p-Cl —CH₂CH₂OCH₃ 417 CH₃ H p-Cl —CH₂CO—OCH₃ 418 CH₃ H p-Cl —CH₂CH₂CO—OCH₃ 419 CH₃ H p-Br —CH₃ 420 CH₃ H p-Br —C₂H₅ 421 CH₃ H p-Br n-C₃H₇ 422 CH₃ H p-Br —CH₂CH₂COH₃ 423 CH₃ H p-Br —CH₂CO—OCH₃ 424 CH₃ H p-Br —CH₂CH₂CO—OCH₃ 425 CH₃ H p-NO₂ —CH₃ 426 CH₃ H p-NO₂ —C₂H₅ 427 CH₃ H p-NO₂ n-C₃H₇ 428 CH₃ H p-NO₂ —CH₂CH₂OCH₃ 429 CH₃ H p-NO₂ —CH₂CO—OCH₃ 430 CH₃ H p-NO₂ —CH₂CH₂CO—OCH₃ 430 CH₃ H H —CH₃ 432 CH₃ H H —C₂H₅ 433 CH₃ H H n-C₃H₇ 434 CH₃ H H —CH₂CH₂OCH₃ 435 CH₃ H H —CH₂CO—OCH₃ 436 CH₃ H H —CH₂CH₂CO—OCH₃ 437 OCH₃ H m-NO₂ —CH₃ 438 OCH₃ H m-NO₂ —C₂H₅ 439 OCH₃ H m-NO₂ n-C₃H₇ 440 OCH₃ H m-NO₂ —CH₂CH₂OCH₃ 441 OCH₃ H m-NO₂ —CH₂CO—OCH₃ 442 OCH₃ H m-CF₃ —CH₂CH₂CO—OCH₃ 443 OCH₃ H m-CF₃ —CH₃ 444 OCH₃ H m-CF₃ —C₂H₅ 445 OCH₃ H m-CF₃ n-C₃H₇ 446 OCH₃ H m-CF₃ —CH₂CH₂OCH₃ 447 OCH₃ H m-CF₃ —CH₂CO—OCH₃ 448 OCH₃ H m-CF₃ —CH₂CH₂CO—OCH₃ 449 OCH₃ H p-OCH₃ —CH₃ 450 OCH₃ H p-OCH₃ —C₂H₅ 451 OCH₃ H p-OCH₃ n-C₃H₇ 452 OCH₃ H p-OCH₃ —CH₂CH₂OCH₃ 453 OCH₃ H p-OCH₃ —CH₂CO—OCH₃ 454 OCH₃ H p-OCH₃ —CH₂CH₂CO—OCH₃ 455 OCH₃ H p-CN —CH₃ 456 OCH₃ H p-CN —C₂H₅ 457 OCH₃ H p-CN n-C₃H₇ 458 OCH₃ H p-CN —CH₂CH₂COH₃ 459 OCH₃ H p-CN —CH₂CO—OCH₃ 460 OCH₃ H p-CN —CH₂CH₂CO—OCH₃ 461 OCH₃ H p-Cl —CH₃ 462 OCH₃ H p-Cl —C₂H₅ 463 OCH₃ H p-Cl n-C₃H₇ 464 OCH₃ H p-Cl —CH₂CH₂OCH₃ 465 OCH₃ H p-Cl —CH₂CO—OCH₃ 466 OCH₃ H p-Cl —CH₂CH₂CO—OCH₃ 467 OCH₃ H p-Br —CH₃ 468 OCH₃ H p-Br —C₂H₅ 469 OCH₃ H p-Br n-C₃H₇ 470 OCH₃ H p-Br —CH₂CH₂OCH₃ 471 OCH₃ H p-Br —CH₂CO—OCH₃ 472 OCH₃ H p-Br —CH₂CH₂CO—OCH₃ 473 OCH₃ H p-NO₂ —CH₃ 474 OCH₃ H p-NO₂ —C₂H₅ 475 OCH₃ H p-NO₂ n-C₃H₇ 476 OCH₃ H p-NO₂ —CH₂CH₂OCH₃ 477 OCH₃ H p-NO₂ —CH₂CO—OCH₃ 478 OCH₃ H p-NO₂ —CH₂CH₂CO—OCH₃ 479 OCH₃ H H —CH₃ 480 OCH₃ H H —C₂H₅ 481 OCH₃ H H n-C₃H₇ 482 OCH₃ H H —CH₂CH₂OCH₃ 483 OCH₃ H H —CH₂CO—OCH₃ 484 OCH₃ H H —CH₂CH₂CO—OCH₃ 485 CF₃ H m-NO₂ —CH₃ 486 CF₃ H m-NO₂ —C₂H₅ 487 CF₃ H m-NO₂ n-C₃H₇ 488 CF₃ H m-NO₂ —CH₂CH₂COH₃ 489 CF₃ H m-NO₂ —CH₂CO—OCH₃ 490 CF₃ H m-CF₃ —CH₂CH₂CO—OCH₃ 491 CF₃ H m-CF₃ —CH₃ 492 CF₃ H m-CF₃ —C₂H₅ 493 CF₃ H m-CF₃ n-C₃H₇ 494 CF₃ H m-CF₃ —CH₂CH₂COH₃ 495 CF₃ H m-CF₃ —CH₂CO—OCH₃ 496 CF₃ H m-CF₃ —CH₂CH₂CO—OCH₃ 497 CF₃ H p-OCH₃ —CH₃ 498 CF₃ H p-OCH₃ —C₂H₅ 499 CF₃ H p-OCH₃ n-C₃H₇ 500 CF₃ H p-OCH₃ —CH₂CH₂OCH₃ 501 CF₃ H p-OCH₃ —CH₂CO—OCH₃ 502 CF₃ H p-OCH₃ —CH₂CH₂CO—OCH₃ 503 CF₃ H p-CN —CH₃ 504 CF₃ H p-CN —C₂H₅ 505 CF₃ H p-CN n-C₃H₇ 506 CF₃ H p-CN —CH₂CH₂OCH₃ 507 CF₃ H p-CN —CH₂CO—OCH₃ 508 CF₃ H p-CN —CH₂CH₂CO—OCH₃ 509 CF₃ H p-Cl —CH₃ 510 CF₃ H p-Cl —C₂H₅ 511 CF₃ H p-Cl n-C₃H₇ 512 CF₃ H p-Cl —CH₂CH₂OCH₃ 513 CF₃ H p-Cl —CH₂CO—OCH₃ 514 CF₃ H p-Cl —CH₂CH₂CO—OCH₃ 515 CF₃ H p-Br —CH₃ 516 CF₃ H p-Br —C₂H₅ 517 CF₃ H p-Br n-C₃H₇ 518 CF₃ H p-Br —CH₂CH₂OCH₃ 519 CF₃ H p-Br —CH₂CO—OCH₃ 520 CF₃ H p-Br —CH₂CH₂CO—OCH₃ 521 CF₃ H p-NO₂ —CH₃ 522 CF₃ H p-NO₂ —C₂H₅ 523 CF₃ H p-NO₂ n-C₃H₇ 524 CF₃ H p-NO₂ —CH₂CH₂COH₃ 525 CF₃ H p-NO₂ —CH₂CO—OCH₃ 526 CF₃ H p-NO₂ —CH₂CH₂CO—OCH₃ 527 CF₃ H H —CH₃ 528 CF₃ H H —C₂H₅ 532 529 CF₃ H H n-C₃H₇ 530 CF₃ H H —CH₂CH₂COH₃ 531 CF₃ H H —CH₂CO—OCH₃ 532 CF₃ H H —CH₂CH₂CO—OCH₃ 533 Br H m-CF₃ —C₂H₅ 534 Br H m-CF₃ n-C₃H₇ 535 Br H m-CF₃ —CH₂CH₂COH₃ 536 Br H m-CF₃ —CH₂CO—OCH₃ 537 Br H m-CF₃ —CH₂CH₂CO—OCH₃ 538 Br H p-OCH₃ —CH₃ 539 Br H p-OCH₃ —C₂H₅ 540 Br H p-OCH₃ n-C₃H₇ 541 Br H p-OCH₃ —CH₂CH₂OCH₃ 542 Br H p-OCH₃ —CH₂CO—OCH₃ 543 Br H p-OCH₃ —CH₂CH₂CO—OCH₃ 544 Br H p-CN —CH₃ 545 Br H p-CN —C₂H₅ 546 Br H p-CN n-C₃H₇ 547 Br H p-CN —CH₂CH₂OCH₃ 548 Br H p-CN —CH₂CO—OCH₃ 549 Br H p-CN —CH₂CH₂CO—OCH₃ 550 Br H p-Cl —CH₃ 551 Br H p-Cl —C₂H₅ 552 Br H p-Cl n-C₃H₇ 553 Br H p-Cl —CH₂CH₂OCH₃ 554 Br H p-Cl —CH₂CO—OCH₃ 555 Br H p-Cl —CH₂CH₂CO—OCH₃ 556 Br H p-Br —CH₃ 557 Br H p-Br —C₂H₅ 558 Br H p-Br n-C₃H₇ 559 Br H p-Br —CH₂CH₂OCH₃ 560 Br H p-Br —CH₂CO—OCH₃ 561 Br H p-Br —CH₂CH₂CO—OCH₃ 562 Br H p-NO₂ —CH₃ 563 Br H p-NO₂ —C₂H₅ 564 Br H p-NO₂ n-C₃H₇ 565 Br H p-NO₂ —CH₂CH₂OCH₃ 566 Br H p-NO₂ —CH₂CO—OCH₃ 567 Br H p-NO₂ —CH₂CH₂CO—OCH₃ 568 Br H H —CH₃ 569 Br H H —C₂H₅ 570 Br H H n-C₃H₇ 571 Br H H —CH₂CH₂OCH₃ 572 Br H H —CH₂CO—OCH₃ 573 Br H H —CH₂CH₂CO—OCH₃ 574 Br H m-NO₂ —CH₃ 575 Br H m-NO₂ —C₂H₅ 576 Br H m-NO₂ n-C₃H₇ 577 Br H m-NO₂ —CH₂CH₂OCH₃ 578 Br H m-NO₂ —CH₂CO—OCH₃ 579 Br H m-CF₃ —CH₂CH₂CO—OCH₃ 580 Br H m-CF₃ —CH₃

II. APPLICATION EXAMPLES

II .1: Dyeing of Polyester

1 part by weight of the dye of formula (101) prepared in Example 1.1 is milled together with four parts of a commercially available dispersing agent and 15 parts of water. Using that formulation, a 1% dyeing (based on the dye and the substrate) is produced on woven polyester by high temperature exhaust process at 135° C.

Test results: the light fastness of the dyeing is excellent as well as the results in the AATCC 61 and ISO 105 tests. The build up properties of the dye are very good. 

1. A dye of formula

wherein R₁ is bromo, nitro, cyano, methyl, methoxy or trifluoromethyl; R₂ is hydrogen, chloro, bromo or trifluoromethyl; R₃ is hydrogen, chloro, bromo, methoxy, trifluoromethyl, nitro or cyano; and R₄ is methyl, ethyl, n-propyl, 2-methoxyethyl, methoxycarbonylmethyl or 2-methoxycarbonylethyl; with the proviso that R₁ is cyano when R₂ is chloro or bromo, and R₁ is cyano or nitro when R₂ is trifluoromethyl.
 2. The dye of formula (1) according to claim 1, wherein R₁ is cyano.
 3. The dye of formula (1) according to claim 2, wherein R₂ is chloro.
 4. The dye of formula (1) according to claim 1, wherein R₃ is hydrogen.
 5. The dye of formula (1) according to claim 1, wherein R₄ is methyl, ethyl, methoxycarbonylmethyl or 2-methoxycarbonylethyl.
 6. A process for the preparation of the dye of formula (1) according to claim 1, which comprises diazotising a compound of formula

and coupling the diazonium compound so obtained to a coupling component of formula

wherein R₁, R₂, R₃ and R₄ have the meanings given for formula (1) in claim
 1. 7. A dye mixture comprising at least one dye of formula (1) according to claim 1 and at least one further dye selected from the group consisting of C.I. Disperse Blue 60, C.I. Disperse Blue 79:1, C.I. Disperse Blue 72:2, C.I. Disperse Blue 148, C.I. Disperse Blue 149, C.I. Disperse Blue 165, C.I. Disperse Blue 165:1, C.I. Disperse Blue 207, C.I. Disperse Blue 284, C.I. Disperse Blue 295, C.I. Disperse Blue 316, C.I. Disperse Blue 337, C.I. Disperse Blue 354, C.I. Disperse Blue 366, C.I. Disperse Blue 367, C.I. Disperse Blue 368, C.I. Disperse Blue 376, C.I. Disperse Blue 378, C.I. Disperse Blue 380, C.I. Disperse Green 9, C.I. Disperse Violet 107, the compounds of formulas (101)-(179) described in WO 2014/016072, the compounds of formulas (101)-(106) described in WO 2009/013122 and the compounds of formulas II-2, II -3, II-4 and III-1-III-8 described in CN
 101955691. 8. A process for dyeing or printing semi-synthetic or synthetic hydrophobic fibre material which comprises applying to or incorporating into the hydrophobic fibre material at least one dye of formula (1) according to claim 1 or the dye mixture according to claim
 7. 9. A process according to claim 8, wherein the hydrophobic fibre material contains polyester fibres.
 10. A material dyed or printed according to either claim 8 or claim
 9. 